CN110520298A - It can be used for manufacturing the lip supports object of object by increasing material manufacturing - Google Patents

It can be used for manufacturing the lip supports object of object by increasing material manufacturing Download PDF

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Publication number
CN110520298A
CN110520298A CN201880020323.3A CN201880020323A CN110520298A CN 110520298 A CN110520298 A CN 110520298A CN 201880020323 A CN201880020323 A CN 201880020323A CN 110520298 A CN110520298 A CN 110520298A
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CN
China
Prior art keywords
carrier board
segment
contact
weight
item methods
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201880020323.3A
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Chinese (zh)
Inventor
G.W.达克斯二世
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Carbon Co Ltd
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Carbon Co Ltd
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Publication date
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Publication of CN110520298A publication Critical patent/CN110520298A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B29C64/124—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/10—Formation of a green body
    • B22F10/12—Formation of a green body by photopolymerisation, e.g. stereolithography [SLA] or digital light processing [DLP]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/40—Structures for supporting workpieces or articles during manufacture and removed afterwards
    • B22F10/47—Structures for supporting workpieces or articles during manufacture and removed afterwards characterised by structural features
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/60—Treatment of workpieces or articles after build-up
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/20—Apparatus for additive manufacturing; Details thereof or accessories therefor
    • B29C64/245—Platforms or substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/40—Structures for supporting 3D objects during manufacture and intended to be sacrificed after completion thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
    • B33Y40/20—Post-treatment, e.g. curing, coating or polishing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y80/00—Products made by additive manufacturing
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/25—Process efficiency

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Optics & Photonics (AREA)

Abstract

A kind of method manufacturing three-dimension object is the following steps are included: (a) provides carrier board (15) and the optical clear component (12) with building surface, the carrier board and the building surface limit building region between them, wherein the building surface has polymerizable liquid above it；(b) by following steps manufactured on the carrier board object (such as, central object (31b)): the building region is irradiated with the light across the optical clear component and also promotes the carrier board and the building surface away from each other, continuous liquid interface is maintained between the carrier board and the central object of growth simultaneously, wherein: (i) described object includes carrier board contact-segment, and the contact-segment includes marginal portion；(ii) described object further includes the lip supports object (34b) extended outward from the contact-segment marginal portion from the contact-segment, wherein the lip supports object forms on the carrier board and at least partially surrounding the contact-segment.

Description

It can be used for manufacturing the lip supports object of object by increasing material manufacturing
Related application
This application claims the priority for the U.S. Provisional Application No. 62/475,496 that on March 23rd, 2017 submits, the interim Shens Disclosure please is whole incorporated herein with it by reference.
Invention field
Present invention relates generally to increasing material manufacturings, and relate more specifically to method, wherein by antelabium during increasing material manufacturing Supporter (lip support) is added on object with object during reducing increasing material manufacturing from the removing on carrier board.
Background
In traditional increasing material manufacturing or three-dimensional manufacturing technology, implement the building of three-dimension object in a manner of gradually or successively.It is typical Ground is solidified under the action of visible light or UV light irradiate by light-curable resin and is formed come implementation level.Commonly referred to as " solid is flat Version printing (stereolithography) ", two kinds of special technologies are it is known that one is the top surfaces of the object in growth Upper formation mew layer；Another kind is to form mew layer on the bottom surface of the object of growth.The example of such method includes the beauty of Hull U.S. Patent number 5,391,072 and 5,529,473, the John of state's patent No. 5,236,637 (see, e.g. Fig. 3-4), Lawton U.S. Patent number 7,438,846, the U.S. Patent number 7,892,474 of Shkolnik, El-Siblani U.S. Patent number 8, 110,135, the U.S. Patent Application Publication No. of the U.S. Patent Application Publication No. 2013/0292862 of Joyce and Chen et al. Those of provided in 2013/0295212.
Recently, the technology of referred to as " manufacture of continuous liquid interface " (or " CLIP ") has been developed.These technologies make it possible to Three-dimension object is quickly manufactured in a manner of no layer, can have desirable structural property and mechanical property by its each component.Referring to, Such as J. DeSimone et al., PCT Application No. PCT/US2014/015486 (as 9,211,678 disclosure of U.S. Patent number), PCT/US2014/015506 (as 9,205,601 disclosure of U.S. Patent number), PCT/US2014/015497 are (special as the U.S. Sharp number 9,216,546 disclosures), J. Tumbleston et al.,Continuous liquid interface production of 3D Objects, Science 347,1349-1352 (on March 16th, 2015 is open online) and R. Janusziewcz Et al., Layerless fabrication with continuous liquid interface production,Proc. Natl. Acad. Sci. USA 113,11703-11708 (on October 18th, 2016).
Recently, J. Rolland et al., U.S. Patent number 9,453,142 and U.S. Patent Application Publication No. US 2016/ 0136889, it is described in US 2016/0137838 and US 2016/016077 and is suitable for stereolithography techniques (especially Be suitable for CLIP) dual cure stereolithographic resin.These resins usually include the usually polymerize by light One polymerizable system (sometimes referred to as " part A ") is produced from it central object, and also includes at least the second polymerizable system (" part B ") usually solidifies after being initially formed central object and assigns the desirable structural property of final object and/or drawing Stretch property.
Both development stimulated increasing material manufacturing technique except manufacturing (main) prototype objects in addition to applied to more suitable for The functional object of various final uses.This has generated the various new technical problems for needing solution, for example, as follows It is discussed.
It summarizes
Manufacture three-dimension object method the following steps are included: (a) provide carrier board and with building surface optical clear component, The carrier board and the building surface limit building region between them, wherein have above it can on the building surface Polymeric liquid；(b) object (for example, central object) is manufactured on the carrier board by following steps: with across the light The light for learning transparent component irradiates the building region and also promotes the carrier board and the building surface away from each other, while Continuous liquid interface is maintained between the carrier board and the central object of growth, in which: (i) described object includes carrier board contact Section, the contact-segment includes marginal portion；(ii) described object further includes from the contact-segment outward from the contact-segment side The lip supports object that edge point extends, wherein the lip supports object forms on the carrier board and at least partially surrounding institute State contact-segment.
In some embodiments, the central object is flexible.
In some embodiments, the lip supports object is configured in the propulsion carrier board far from the building table The central object is inhibited to remove during face from the carrier board.
In some embodiments, the lip supports object is configured to towards building surface intermittent pumping (pumping) central object is inhibited to remove from the carrier board during the carrier board.
In some embodiments, the average perimeter of the object increases over time during the manufacturing step At least once.
In some embodiments, the method further includes following steps: object described in (c) optionally washing (for example, With the cleaning solution comprising organic solvent)；Then (d) solidifies the central object further to manufacture the three-dimension object.
The method further comprises after the manufacturing step (b) optionally, but in some embodiments preferably The step of lip supports object is separated with the object.
In some embodiments, the three-dimension object is elastomer.
In some embodiments, at least part of both the central object and described three-dimension object is (for example, at least It is most of) in grid (lattice) or the configuration of net (mesh).
In some embodiments, the polymerizable liquid includes dual cure polymerizable liquid.
In some embodiments, institute is at least partly carried out with reciprocal (reciprocal) (or " pumping ") operation mode State manufacturing step.
In some embodiments, the manufacturing step (b) includes photopolymerization step, and/or by described in heating progress Further curing schedule (d).
In some embodiments, the optical clear component is that polymerization inhibitor can be thoroughly.
In some embodiments, the manufacturing step (b) is carried out by bottom-up stereolithography.
In some embodiments, the manufacturing step (b) is carried out by the manufacture of continuous liquid interface.
In some embodiments, the polymerizable liquid is made up of: (i) can participate in passing through stereolithography The monomer and/or prepolymer for forming the photopolymerization of central object are (preferably with 5 weight %, 10 weight % or 20 weight % to 50 weights Measure %, 60 weight % or 80 weight % amount by comprising)；(ii) can thermal polymerization monomer and/or prepolymer (preferably with 5 weight %, The amount of 10 weight % or 20 weight % to 40 weight %, 50 weight % or 60 weight % by comprising).
In some embodiments, the monomer and/or prepolymer of the photopolymerization include to be selected from acrylate, methyl-prop Olefin(e) acid ester, alpha-olefin, N- vinyl (N-vinyls), acrylamide, Methacrylamide, styrenic (styrenics), epoxides, mercaptan, 1,3- diene, ethylene halide, acrylonitrile, vinyl esters, maleimide and ethylene The reactive terminal group of base ether.
In some embodiments, the polymerizable liquid includes the component of photopolymerization, in its light in step (a) Ingredient needed for degrading after polymerization (for example, heating thereafter) and form the further curing schedule (d).
Another aspect of the present invention is the three-dimension object manufactured on carrier board by increasing material manufacturing, and the object includes: (a) three-dimensional body part, the main part include carrier board contact-segment, and the contact-segment includes marginal portion；(b) and institute The lip supports object stating contact-segment connection and extending outward from the contact-segment marginal portion from the contact-segment, wherein the lip Edge supporter forms on the carrier board and at least partially surrounding the contact-segment.Typically, the lip supports object packet Carrier board contact-segment is included, also, the main part carrier board contact-segment and the lip supports object carrier board contact-segment are coplanar. Typically, it is (described by the lip supports object and the contact-segment to be attached to carrier board for the object (when being initially formed) Object is then removed from the carrier board).
Above and other target of the invention is explained in greater detail in the attached drawing and specification set forth below of this paper And aspect.The disclosure of all U.S. patent references cited herein is all incorporated herein by reference.
Brief description
Fig. 1 schematically illustrates the method and apparatus for manufacturing three-dimension object by continuous liquid interface manufacture (CLIP), Wherein the object is substantially rigid.
Fig. 2 schematically illustrates the method and apparatus for manufacturing three-dimension object by CLIP, wherein the object is It is flexible.
Fig. 3 A is similar to Fig. 2, and stripping seen in Figure 2 is reduced on lip supports object to object except that having added From.
Fig. 3 B is the enlarged view of a part of Fig. 3.
Fig. 4 is another schematic example for manufacturing object by using the CLIP of antistripping antelabium and then removing the antelabium Show.
Fig. 5 is similar to Fig. 4, uses the exemplary object of substitution.
It is described in detail
It is described more fully hereinafter with the present invention referring now to the drawings, shows embodiment of the present invention in the accompanying drawings.So And the present invention can be embodied in many different forms and embody and should not be construed as limited to embodiment set forth herein；Phase Instead, these embodiments are provided so that present disclosure will be detailed and complete, and of the invention by fully communicating Range is to those skilled in the art.
"and/or" includes that correlation lists any of project and all possible combination or one as used herein, the term Or more, and there is no combinations when with alternative ("or") explanation.
1. resin and dual cure resin.
Although any suitable polymerizable liquid (especially photopolymerization liquid as used in stereolithography can be used Body) the implementation present invention, but currently preferred dual cure resin.
It can be used for increasing material manufacturing, be used in particular for the double of stereolithography techniques such as continuous liquid interface manufacture (CLIP) Solidification polymerizable liquid is known and is described in again, for example, J. Rolland et al., PCT application PCT/US2015/036893 (seeing also U.S. Patent Application Publication No. US 2016/0136889), PCT/US2015/036902 (see also United States Patent (USP) Shen Please publication number US 2016/0137838), PCT/US2015/036924 (see also U.S. Patent Application Publication No. US 2016/ 016077) and in PCT/US2015/036946 (seeing also U.S. Patent number 9,453,142).In general, this kind of resin can Include: can (a) form the monomer and/or prepolymer of the photopolymerization of central object (usually in the presence of photochemical catalyst)；(b) Can thermal polymerization monomer and/or prepolymer.As described above, in some embodiments, (c) thermoplastic granulates can be used in these ingredients And/or (d) diels-Alder (Diels-Alder) adduct supplement and/or replacement.These ingredients further described below In each.
A. the monomer and/or prepolymer of photopolymerization.Otherwise referred to as " part A " of resin, these are can to pass through exposure In monomer and/or prepolymer that actinic radiation or light are polymerize.The resin can have 2 or higher degree of functionality (although when poly- It is 1 resin that degree of functionality can also be used when closing object insoluble in monomer).The purpose of part A is that " locking " is formed by object Shape or generate bracket for one or more of additional components (for example, part B).Importantly, part A is to take a picture During lithographic printing after initial solidification, maintains minimum needed for being formed by the shape of object or deposited higher than minimum In.In some embodiments, the amount is corresponding to all resins (polymerizable liquid) composition less than 10 weight %, 20 weight % Or 30 weight %.
The example for being suitable for the suitable reactive terminal group of part A ingredient, monomer or prepolymer includes, but are not limited to: third Olefin(e) acid ester, methacrylate, alpha-olefin, N- vinyl, acrylamide, Methacrylamide, styrenic, epoxidation Object, mercaptan, 1,3- diene, ethylene halide, acrylonitrile, vinyl esters, maleimide and vinyl ethers.
The cured one aspect of part A is that it provides bracket, is known as second reaction resin of " part B " wherein Component can solidify during second step, as discussed further below.
B. can thermal polymerization monomer and/or prepolymer.Otherwise referred to as " part B ", these ingredients may include having in the portion A The monomer of the reactive terminal group of the second curing reaction and/or the mixture of prepolymer are participated in after point curing reaction, by the mixture Composition is substantially made of the mixture.Generally, for dual cure resin, the reality of the method for solidifying part B Example includes, but are not limited to: make object or bracket with hot, water or vapor, with the wavelength different with the wavelength for solidifying part A Light, catalyst (presence or absence of additional heat) contact, boil off from polymerizable liquid solvent (for example, using heat, vacuum or A combination thereof), microwave irradiation etc., including a combination thereof.In this case, the heat cure of " part B " resin is preferred.
The example for being suitable for the suitable reactive terminal group pair of part B ingredient, monomer or prepolymer includes, but are not limited to: Epoxy (epoxy)/amine, epoxy/hydroxyl, oxetanes/amine, oxetanes/alcohol, isocyanates*/ hydroxyl, isocyanates*/ Amine, isocyanates/carboxylic acid, acid anhydrides/amine, amine/carboxylic acid, amine/ester, hydroxyl/carboxylic acid, hydroxyl/acid chloride, amine/acid chloride, ethylene Base/Si-H (hydrosilylation), Si-Cl/ hydroxyl, Si-Cl/ amine, hydroxyl/aldehyde, amine/aldehyde, methylol or methylolamide/ Alcohol, aminoplast (aminoplast), alkynes/azide (also include mercaptan-alkene, Michael's addition, Di Er with addition reaction This-Alder reaction, nucleophilic substitution etc. be known as the embodiment of " click chemistry " together), alkene/sulphur (poly- fourth Diene vulcanization), alkene/peroxide, olefin/mercaptan, alkynes/mercaptan, hydroxyl/halide, isocyanates*/ water (polyurethane foam Foam), it is Si-OH/ hydroxyl, Si-OH/ water, the Si-OH/Si-H silicone of catalysis (tin), Si-OH/Si-OH (silicone of tin catalysis), complete Fluoride-based (coupling is to form Freon C318) etc., wherein * isocyanates includes shielded isocyanates (such as oxime), uses In diene/dienophile of Diels-Alder reaction, olefin metathesis polymerisation, use ziegler-nata (Ziegler- Natta the olefinic polymerization that) is catalyzed, ring-opening polymerisation (including open loop olefin metathesis polymerisation, lactams, lactone, siloxanes, epoxidation Object, cyclic ethers, imines, cyclic ketal etc.) etc..Such as will be noted from the above, " part B " component typically at least includes to react with each other Compound is to (for example, polyisocyanates and polyamines).
C. thermoplastic granulates.Thermoplastic polymer particles as used in this article initially can not below its solution temperature Those of be dissolved in polymerizable liquid, but be dispersed in the liquid." insoluble " refers to completely insoluble as used in this article Polymer beads and both slightly solubility particles, the slightly solubility grain dissolution is so slowly so that they are dispersed in resin Without being dissolved to such degree: so that they cannot function as the particle photopolymerization in resin in three dimensions during mesosome manufactures. Therefore, which initial (initially initially) can disperse rather than dissolve for any reason, and the reason includes But it is not limited to intrinsic unmixability/insoluble, highest critical solution temperature (UCST), crystallizes, be encapsulated in shell, the shell is in high temperature Lower melting/degradation is (for example, wax melts (wax melt), crystal melt (crystal melt), hydrogen bonding, degradation at high temperature Deng).
It optionally, but in some embodiments preferably, may include end by its thermoplastic polymer for forming particle Functional group or reactive group.Suitable functional group or reactive group include, but are not limited to amine, phenol, maleimide and carboxylic Base group.Any one of for various purposes, it may include such reactive group, the purpose include but is not limited to promote base Compatibility and bonding between matter (for example, first and second curable components of dual UV curable paint) and thermoplastic, It can be stably connected with heat-curable component or UV curable component reaction with being formed, it can instantaneous (transiently) and thermosetting property group Point or UV curable component reaction by control mutually separate thermoplastic domain size and in the form of, heat-curable component can be catalyzed Potential catalyst (amine especially blocked with epoxy and cyanate) etc. is served as in solidification.
In general, thermoplastic granulates have 0.5 to 10,20 or 50 micron of average diameter.They can pass through any conjunction Suitable technology, including but not limited to mechanical lapping, cryogenic grinding (cryo milling), spray drying, solidification etc., and screening Or other technologies well known by persons skilled in the art are prepared by thermoplastic polymer.
D. additional resin component.The photoinitiator for including in polymerizable liquid (resin) can be any suitable light-initiated Agent, including I type and II type photoinitiator and including common UV photoinitiator, the example includes but is not limited to such as acetophenone (such as diethoxy acetophenone), phosphine oxide, diphenyl (2,4,6- trimethylbenzoyl) phosphine oxide, phenyl bis- (2,4,6- Trimethylbenzoyl) phosphine oxide (PPO), Irgacure 369 etc..See, e.g. the U.S. Patent number 9 of Rolland et al., 453,142。
The liquid resin or polymerizable material, which can have, is suspended or dispersed in solid particle therein.Depending on manufactured Any suitable solid particle can be used in final products.The particle can be metal, organically/polymerization, it is inorganic or Or mixtures thereof composite material.The particle can be nonconducting, semiconductive or conductive (including metallic conductor and nonmetallic Conductor or polymer conductor)；And the particle can be magnetism, ferromagnetism, paramagnetism or nonmagnetic.The particle, which can have, appoints What suitable shape, including spherical shape, ellipse, cylinder etc..The particle may have any suitable size (for example, average straight Diameter is in 1 nm to 20 μ ms).
The particle may include activating agent or detectable compounds as described below, although these can also equally as discussed below Dissolution (dissolved solubilized) provides in liquid resin.For example, can using magnetic or paramagnetic particle or Nano particle.
The liquid resin, which can have, is dissolved in additional ingredient therein, including pigment, dyestuff, reactive compound or drug Compound, detectable compounds (for example, fluorescence, phosphorescence, radioactive compound) etc., still depending on the specific of manufactured product Purpose.The example of such additional ingredient includes, but are not limited to protein, peptide, nucleic acid (DNA, RNA) such as siRNA, sugar, small Organic compound (drug and class drug compound) etc., including their combination.
Curing agent:Additional component (curing agent) can be used, reacted with the maleimide of release.Any conjunction can be used Suitable curing agent (see, e.g. U.S. Patent number 5,599,856,6,656,979,8,632,654 and 9,3115,698).One In a little embodiments, the curing agent include amine or polyamines (for example, aromatic amine or polyamines, cycloaliphatic amines or polyamines, aliphatic amine or Polyamines such as polyetheramine etc.).
In some embodiments, the curing agent includes mercaptan or polythiol, allyl compound (allyl) or polyenoid Compound (polyallyl) (diallyl compound, triallyl compound), maleimide are (including but not limited to Those of description above and below), vinyl ethers etc..
Suitable mercaptan-hardened dose of particular example includes, but are not limited to 4,4 '-dimercapto diphenyl ethers, 4,4 '-two mercaptos Base biphenyl, trimethylolpropane tris (3-thiopropionate), pentaerythrite four (3-thiopropionate), (the 3- sulfydryl of 1,3,5- tri- Propyl) -1,3,5- triazine -2,4,6- triketone etc..
The example of suitable allyl compound includes, but are not limited to (methyl) allyl acrylate, 2,2 '-diallyls Bisphenol-A and triallyl -1,3,5- triazine -2,4,6- (1H, 3H, 5H)-triketone.
In some embodiments, which includes latent hardening agent (including its mixture): that is, following curing agent: It has hypoergia at a lower temperature and/or is microsolubility at a lower temperature, so that the curing agent at room temperature may be used With more stable, but then it is activated when heated.Numerous examples of latent hardening agent are known (see, e.g. United States Patent (USP) Numbers 8,779,036；See also U.S. Patent number 4,859,761).Special example includes the guanidine and aromatic amine replaced, such as double Cyanamide, benzoguanamine, OTBG o tolylbiguanide, bis- (4- aminophenyl) sulfones (also referred to as diaminodiphenylsulfone: DDS), bis- (3- amino Phenyl) sulfone, 4,4 '-methylene diamines (4,4'-methylenediamine), 1,2- or 1,3- or 1,4- phenylenediamine, bis- (4- ammonia Base phenyl) -1,4- diisopropylbenzene (DIPB) (such as EPON 1061 from Shell), bis- (4- amino -3,5- 3,5-dimethylphenyl) -1,4- Diisopropylbenzene (DIPB) (such as EPON 1062 from Shell), bis- (aminophenyl) ethers, diaminobenzophenone, 2,6- diamino pyrrole Pyridine, 2,4- toluenediamine, diamino-diphenyl propane, 1,5- diaminonaphthalene, dimethylphenylene diamine, the bis- -4- aminobenzene basic rings of 1,1- Hexane, di-2-ethylhexylphosphine oxide (2,6- diethylaniline) (such as LONZACURE M-DEA from Lonza), (2- is different for di-2-ethylhexylphosphine oxide Propyl -6- methylaniline) (such as LONZACURE M-MIPA from Lonza), di-2-ethylhexylphosphine oxide (2,6- diisopropyl aniline) (such as LONZACURE M-DIPA from Lonza), 4- amino-diphenyl-amine, diethyl toluene diamine, phenyl -4,6- diamino Base triazine and lauryl -4,6- diamino triazine.It include N- acylimidazole such as 1- (2 ', 4 ', 6 '-front threes there are also other examples Base benzoyl) -2- phenylimidazole or 1- benzoyl -2 isopropyl imidazole be (see, e.g. U.S. Patent number 4,436,892 With 4,587,311)；Cyanoacetyl compounds such as dicyanogen methyl isophorone acetic acid neopentyl glycol ester, N- isobutyl cyanide yl acetamide, 1,6- Hexamethylene bis cyan-acetic ester or 1,4-CHDM dicyanogen methyl isophorone acetic acid esters (see, e.g. U.S. Patent number 4,283, 520)；N- Cyano amides compound such as N, N '-dicyano adipamide (see, e.g. U.S. Patent number 4,529,821, 4,550,203 and 4,618,712)；Acyl group thiopropyl phenol (see, e.g. U.S. Patent number 4,694,096) and urea derivative Such as Toluene-2,4-diisocyanate, 4- bis- (N, N- dimethyl carbonyl diamide) (see, e.g. U.S. Patent numbers 3,386,955)；And aliphatic series or Alicyclic diamine and polyamines (if their enough inertia).The example that can be mentioned that herein is polyetheramine, such as JEFFAMINE 230 and 400.Can also be used its reactivity by space and/or electronic effect factor reduce or/and for microsolubility or there is height The aliphatic series or alicyclic diamine or polyamines of fusing point, such as JEFFLINK 754 (Huntsman) or CLEARLINK 1000 (Dorf Ketal)。
Dyestuff/non-reacted light absorber. In some embodiments, include for carrying out polymerizable liquid of the invention Absorb the non-reacted pigments or dyes of light, particularly UV light.The suitable example of such light absorber includes, but are not limited to: (i) titanium dioxide (for example, with 0.05 weight % or 0.1 weight % to the amount of 1 weight % or 5 weight % by comprising), (ii) carbon black (example Such as, with 0.05 weight % or 0.1 weight % to the amount of 1 weight % or 5 weight % by comprising), and/or (iii) organic ultraviolet light absorption Agent for example dihydroxy benaophenonel, hydroxy phenyl benzotriazole, oxanilide, benzophenone, thioxanthones, hydroxyphenyltriazinuv and/ Or benzotriazole UV absorbers (such as Mayzo BLS1326) are (for example, with 0.001 weight % or 0.005 weight % to 1 weight Measure %, 2 weight % or 4 weight % amount by comprising).It is special that the example of suitable organic ultraviolet light absorber includes, but are not limited to the U.S. Sharp number 3,213,058,6,916,867,7,157,586 and 7, described in 695,643 those, the disclosure is logical Cross quote it is incorporated herein.
Filler. Depending on property needed for component or object to be manufactured, can be used about the present invention any suitable Filler.Therefore, filler can be solid or liquid, organic or inorganic, and may include reactivity and non-reacted rubber: silicon Oxygen alkane, acrylonitrile-butadiene rubber；Reactive and non-reacted thermoplastic (including but not limited to: poly- (etherimide), Maleimide-styrene copolymer, polyarylate, polysulfones and polyether sulfone etc.), inorganic filler such as silicate it is (such as sliding Stone, clay, silica, mica), glass, carbon nanotube, graphene, Cellulose nanocrystal body etc., including all above-mentioned groups It closes.Suitable filler includes toughener, for example, core shell rubber as discussed below.
Toughener. One or more polymerization and/or inorganic toughener can be used as filler in the present invention.Referring generally to beauty State's patent application publication number 20150215430.The toughener can be evenly distributed in cured product in granular form.Described The diameter of grain is smaller than 5 microns (μm).Such toughener those of includes, but are not limited to be formed by following substance: elastomer, branch Fluidized polymer, dissaving polymer, dendrimers, rubber-like polymer, rubbery copolymer, block copolymer, core-shell structure copolymer (such as carbon black, carbon are received for grain, oxide or inorganic material such as clay, polyhedral oligomeric silsesquioxane (POSS), carbonaceous material Mitron, carbon nano-fiber, fullerene), ceramics and silicon carbide, with and without surface modification or functionalization.
Core shell rubber 。Core shell rubber is the bulk material (particle) with rubber-like core.Such material be it is known simultaneously It is described in, such as 20150240113 He of U.S. Patent Application Publication No. 20150184039 and U.S. Patent Application Publication No. In U.S. Patent number 6,861,475,7,625,977,7,642,316,8,088,245 and other places.In some embodiments In, core shell rubber particle is nano particle (that is, having the average particle size less than 1000 nanometers (nm)).In general, core shell rubber The average particle size of nano particle is, for example, less than 300 nm, less than 200 nm, less than 100 nm or be even less than less than 500 nm 50 nm.Typically, such particle is spherical, therefore granularity is diameter；However, if fruit granule is not spherical, then granularity quilt It is defined as the longest dimension of particle.Suitable core shell rubber includes, but are not limited to by Kaneka Corporation with title Those of Kaneka Kane Ace sale, the product including 15 and 120 series of Kaneka Kane Ace, including Kanaka Kance Ace MX 120、Kaneka Kane Ace MX 153、Kaneka Kane Ace MX 154、Kaneka Kane Ace MX 156, Kaneka Kane Ace MX170 and Kaneka Kane Ace MX 257 and Kaneka Kane Ace 120 core shell rubber dispersion of MX and its mixture.
In some embodiments, the dual cure resin can be Carbon, Inc. rigid olyurethane resin (RPU), Flexible polyurethane resin (FPU) or elastomer polyurethane resin (EPU), available from Carbon, Inc., 1089 Mills Way, Redwood City, California 94063 USA。
2. increasing material manufacturing method and apparatus.
It is preferred that by increasing material manufacturing, usually bottom-up increasing material manufacturing (commonly referred to as stereolithography) You Keju Resin forms central object.Such method be U.S. Patent number 5,236,637 that is known and being described in such as Hull, The beauty of the U.S. Patent number 5,391,072 and 5,529,473 of Lawton, the U.S. Patent number 7,438,846 of John, Shkolnik The U.S. Patent Application Publication No. of state's patent No. 7,892,474, the U.S. Patent number 8,110,135 of El-Siblani, Joyce In the U.S. Patent Application Publication No. 2013/0295212 of 2013/0292862 and Chen et al..Such technology, which is usually directed to, makes light It is projected through window, in window upper carry resin (or polymerizable liquid) pond.Universal support be usually located above window and Above pond, the object of growth is manufactured on this carrier.In the present invention, the first component plays a part of carrier and at least partly It immerses as in resin pool described above and below.
In some embodiments of the present invention, central object is formed by continuous liquid interface manufacture (CLIP).CLIP It is known and is described in such as PCT Application No. PCT/US2014/015486 (on December 15th, 2015 as United States Patent (USP) Number 9,211,678 disclosures)；PCT/US2014/015506 (is also used as U.S. Patent number 9,205,601 on December 8th, 2015 Openly), PCT/US2014/015497 (being also used as 9,216,546 disclosure of U.S. Patent number on December 22nd, 2015) and J. Tumbleston, D. Shirvanyants, N. Ermoshkin et al., Continuous liquid interface production of 3D Objects, Science In 347,1349-1352 (on March 16th, 2015 is open online).Also Referring to R. Janusziewcz et al., Layerless fabrication with continuous liquid interface production, Proc. Natl. Acad. Sci. USA 113,11703-11708 (on October 18th, 2016).One In a little embodiments, CLIP but is irradiated and/or described using the feature of bottom-up three-dimensional manufacture as described above While forward step, stable or lasting liquid circle is also maintained between the object of growth and building surface or window simultaneously Face, such as in the following manner: (i) persistently maintains the dead zone of polymerizable liquid to contact with the building surface, and (ii) continues Maintain the gradient (such as active surface) of the polymeric area contacted between dead zone and solid polymer and with each, the polymeric area Gradient include in partially cured form the first component.
In some embodiments of CLIP, the optical clear component includes semi permeability component (such as fluoropolymer Object), and by by polymerization inhibitor charging by the optical clear component carry out continue maintain dead zone, thus dead zone and times It is selected in generation inhibitor gradient at least part of the gradient of polymeric area.It can be used for the present invention and potentially no longer to need Other methods of the progress CLIP of semi permeability " window " or window structure are including the use of the liquid surface (ginseng comprising immiscible liquid See L. Robeson et al., WO on October 29th, 2015/164234,2015 is open), generate by electrolysis oxygen as inhibiting Agent (referring to I. Craven et al., WO on August 25th, 2016/133759,2016 open) and by can magnetic force positioning particle (light Activator is in connection) be integrated in polymerizable liquid (referring to J. Rolland, WO on September 15th, 2016/145182,2016 It is open).
In some embodiments, increasing material manufacturing device can be the Carbon, Inc. of implementation continuous liquid interface manufacture M1 device, available from Carbon, Inc., 1089 Mills Way, Redwood City, California 94063 USA。
3. using the increasing material manufacturing of lip supports object.
Fig. 1 schematically illustrates the typical method for manufacturing three-dimension object by continuous liquid interface manufacture (CLIP) And device.The device include with the micro mirror array such as laser light source of light engine 11 that operationally (operatively) is connect, or Scanning laser is projected through optical clear window 12 and enters polymerizable liquid 21.Carrier platform 15 and elevator and driving Sub-assembly 14 is operably connected, and the elevator and drive assembly 14 are operably connected together with light engine with controller 13 (in an alternate embodiment, window and light engine can be lowered far from fixed carrier platform).By being projected from light engine 11 The 3d object 31 (being rigid in this case) that is increased by the photopolymerization manufacture of polymerizable liquid 21 of light, wherein carrier is flat Platform and window are pushed into away from each other and the contact-segment 32 of 3d object 31 is attached on carrier platform.In the embodiment of illustration In, which is carried out by continuous liquid interface manufacture (being described above), thus in the object 31 and polymerizable liquid 21 of growth Between maintain continuous liquid interface 22, such as by maintaining the dead zone of non-polymeric liquid between window and polymerizable liquid (not Display) (or electrochemically, or by using immiscible liquid, or other means by carrying out CLIP as described above) It carries out.
Fig. 2 schematically illustrates the method and apparatus for manufacturing three-dimension object by CLIP, and is retouched as shown in figure 1 That states is essentially identical, except that the 3d object 31a increased is flexible.Notice the contact-segment 32a and carrier in object It is peeling-off between platform, cause gap to be formed.The gap can reduce the efficiency or speed of manufacturing process, and in some cases Under manufacturing process can be caused to fail.
Fig. 3 A-3B is similar to Fig. 2, except that by antistripping lip supports object 34b along contact-segment marginal portion At least part of 33b is added to object 31b to reduce removing seen in Figure 2.It notices in Fig. 2, the left side of object On removing it is more significant, overhang (overhang) of object is bigger at this.Therefore, in Fig. 3, lip supports object is added To the left side of object.It is not intended to be entangled in any specific theory of the invention, it is believed that building plate or " window " and the object increased Suction force between body leads to the anticlockwise torque of the attachment surface relative to component.That is, in some embodiment party (such as " pumping " or " reciprocal " operation mode, wherein the component increased is intermittently promoted towards window to promote to set in case Rouge flows into building region), the power of driving object towards window can have opposite effect, thus on another (right side) side of object Lip supports object can also have value.
As being seen more clearly in the enlarged view of Fig. 3 B, the average width dimension of lip supports object(w)Typically larger than The mean depth size of lip supports object(d)(e.g. twice, three times, five times or ten times big, or bigger), in order to manufacture It is removed it after object from object.Although lip supports object may be frangible in itself or can be with object point since its is relatively thin From, but close to the contact-segment marginal portion 33b of object in lip supports object, that is, right vertical dotted line intersection in figure 3b Point at may include score line, perforation etc..
Fig. 4 is another example for manufacturing object 31c by using the CLIP of antistripping antelabium 34c and then removing the antelabium Show.It also includes antistripping antelabium 34d that Fig. 5, which is similar to Fig. 4 using the exemplary object 31d of substitution,.In both embodiment party In case, manufactured object is usually substantially conical (for frustum) or gradually receives on cross-sectional area in shape Contracting, wherein lesser cross-sectional area is close to carrier platform.When with carrier platform (to the carrier platform to The carrier platform) initial contact (and attachment) area (32c, 32d) compare, manufactured object is in the manufacture phase Between when increasing at least once in total side surface area of contact window, which shows special value.
4. step after manufacture.
After being manufactured by increasing material manufacturing, 3d object can be further processed, usually by washing and --- Using some dual cure resins as polymerizable liquid --- by further solidifying (such as passing through heating) It carries out.
Washing.After forming central object, optionally it is washed (such as with organic solvent), optionally drying (such as Air-dry) and/or rinse (with random order).
It can be used for implementing solvent of the invention (or " cleaning solution ") and include, but are not limited to water, organic solvent and combinations thereof (example Such as, group is combined into cosolvent), optionally contain additional ingredient, such as surfactant, chelating agent (ligand), enzyme, borax, dyestuff Or colorant, fragrance etc., including a combination thereof.Cleaning solution can be in any suitable form, such as solution, lotion, dispersion liquid etc..
The example that can be used as the organic solvent of cleaning solution or the ingredient as cleaning solution includes, but are not limited to alcohol, ester, divalent Acid esters, ketone, acid, aromatic hydrocarbon, ether, dipolar aprotic, halogenation and alkali organic solvent, including a combination thereof.Solvent can be based partially on it Environment and health effect select (see, e.g. GSK Solvent Selection Guide 2009).Additional reality Example includes hydrofluorocarbon solvent (for example, 1,1,1,2,3,4,4,5,5,5- Decafluoropentane (Vertrel XF, DuPontTM Chemours), 1,1,1,3,3- pentafluoropropane, 1,1,1,3,3-pentafluorobutane etc.)；Chloro fluorocarbon solvent is (for example, 3,3- bis- is chloro- 1,1,1,2,2- pentafluoropropane, the chloro- 1,1,2,2,3- pentafluoropropane of 1,3- bis-, the chloro- 1- fluoroethane of 1,1- bis- etc.)；Hydrofluoroether is molten Agent is (for example, methyl nonafluorobutyl ether (HFE-7100), nine fluorine isobutyl ether (HFE-7100) of methyl, ethyl no nafluoro butyl ether (HFE-7200), nine fluorine isobutyl ether (HFE-7200) of ethyl, tetra- fluoro ethyl -2,2,2- trifluoroethyl ether of 1,1,2,2- etc.)；It waves Hair property methylsiloxane solvent is (for example, hexamethyldisiloxane (OS-10, Dow Corning), octamethyltrisiloxane (OS- 20, Dow Corning), decamethyl tetrasiloxane (OS-30, Dow Corning) etc.), including its mixture.
It can be used any suitable cleaning device, including but not limited to U.S. Patent number 5,248,456,5,482,659,6, 660,208, described in 6,996,245 and 8,529,703 those.
Further solidification.Although can be by any suitable technology (including but not limited in U.S. Patent number 9,453,142 Those of description) further (or second) solidification is carried out, in preferred embodiments, further solidified by heating.
Heating can be actively heating (for example, in an oven, such as electricity, coal gas, solar energy baking oven or micro-wave oven or its group Close) or passive heating (for example, at ambient temperature).Actively heating will be usually than passively heating more rapidly and in some implementations Preferred in scheme, but passive heating --- for example simply make intermediate maintain sufficient at ambient temperature time with Realize further solidification --- it is preferred in some embodiments.
In some embodiments, heating stepses are carried out at a temperature of at least first (baking oven) temperature and second (baking oven), Wherein the first temperature is greater than environment temperature, and second temperature is greater than the first temperature, and second temperature is lower than 300 °C (for example, in ring There is ramp type or staged to improve) between border temperature and the first temperature and/or between the first temperature and second temperature.One In a little embodiments, heating stepses are carried out at a temperature of at least first (baking oven) temperature and second (baking oven), wherein the first temperature Greater than environment temperature, second temperature is greater than the first temperature, and second temperature is lower than 300 °C (for example, in environment temperature and first There is ramp type or staged to improve) between temperature and/or between the first temperature and second temperature.
For example, can be with stepwise manner at a first temperature of about 70 DEG C to about 150 DEG C, and then at about 150 DEG C to 200 Or heating intermediate under 250 DEG C of second temperature, wherein the duration heated every time depends on size, the shape of the intermediate And/or thickness.In another embodiment, intermediate can be solidified by ramp type heating schedule, wherein temperature is from environment temperature Pass through 70 to 150 DEG C of temperature with 0.5 DEG C/min to 5 DEG C/min of rate of heat addition variation oblique ascension, and up to 250 or 300 DEG C Final (baking oven) temperature (see, e.g. U.S. Patent number 4,785,075).
Once completing further curing schedule, implementable any conventional post-processing step (is further cleaned, is cut, grinding Mill etc.), and by object pack or with other components assembling be used for deliver or for their intended use.
Above-mentioned is illustration of the invention, and should not be construed as its limitation.The present invention is determined by the claims that follow, and right is wanted The equivalent asked is included in wherein.

Claims (23)

1. a kind of method for manufacturing three-dimension object, the described method comprises the following steps:
(a) carrier board and the optical clear component with building surface are provided, the carrier board and the building surface are at them Between limit building region, wherein the building surface has polymerizable liquid above it；With
(b) object (for example, central object) is manufactured on the carrier board by following steps: with across the optical clear structure The light of part irradiates the building region and also promotes the carrier board and the building surface away from each other, while in the carrier Continuous liquid interface is maintained between plate and the central object of growth, in which:
(i) object includes carrier board contact-segment, and the contact-segment includes marginal portion；With
(ii) object further includes the lip supports object extended outward from the contact-segment marginal portion from the contact-segment, Described in lip supports object formed on the carrier board and at least partially surrounding the contact-segment.
2. method described in claim 1, wherein the central object is flexible.
3. method of any of claims 1 or 2, wherein the lip supports object is configured in the propulsion carrier board far from institute The central object is inhibited to remove from the carrier board during stating building surface.
4. the described in any item methods of preceding claims, wherein the lip supports object is configured to towards the building surface The central object is inhibited to remove during carrier board described in intermittent pumping from the carrier board.
5. the described in any item methods of preceding claims, wherein during the manufacturing step object average perimeter with The past of time increases at least once.
6. the described in any item methods of preceding claims, further include steps of
(c) object described in optionally washing (for example, with cleaning solution comprising organic solvent)；Then
(d) solidify the central object further to manufacture the three-dimension object.
7. the described in any item methods of preceding claims further comprise after the manufacturing step (b) by the antelabium The step of supporter is separated with the object.
8. the described in any item methods of preceding claims, wherein the three-dimension object is elastomer.
9. the described in any item methods of preceding claims, wherein at least the one of both the central object and described three-dimension object Partially (for example, at least most of) is in grid or the configuration of net.
10. the described in any item methods of preceding claims, wherein the polymerizable liquid includes dual cure polymerizable liquid.
11. the described in any item methods of preceding claims, wherein at least partly with reciprocal (or " pumping ") operation mode into The row manufacturing step.
12. the described in any item methods of preceding claims, in which:
The manufacturing step (b) includes photopolymerization step, and/or
The further curing schedule (d) is carried out by heating.
13. the described in any item methods of preceding claims, wherein the optical clear component is that polymerization inhibitor can be thoroughly.
14. the described in any item methods of preceding claims, wherein carrying out the system by bottom-up stereolithography Make step (b).
15. the described in any item methods of preceding claims, wherein carrying out the manufacturing step by the manufacture of continuous liquid interface (b)。
16. the described in any item methods of preceding claims, wherein the polymerizable liquid is made up of:
(i) can participate in by stereolithography formed central object photopolymerization monomer and/or prepolymer (preferably with The amount of 5 weight %, 10 weight % or 20 weight % to 50 weight %, 60 weight % or 80 weight % by comprising)；
(ii) can thermal polymerization monomer and/or prepolymer (preferably with 5 weight %, 10 weight % or 20 weight % to 40 weight %, 50 weights Measure % or 60 weight % amount by comprising).
17. method described in claim 16, wherein the monomer and/or prepolymer of the photopolymerization include to be selected from acrylic acid Ester, methacrylate, alpha-olefin, N- vinyl, acrylamide, Methacrylamide, styrenic, epoxides, Mercaptan, 1,3- diene, ethylene halide, acrylonitrile, vinyl esters, maleimide and vinyl ethers reactive terminal group.
18. method described in claim 16 or 17, wherein it is described can thermal polymerization monomer and/or prepolymer include selected from following Reactive terminal group: epoxy/amine, epoxy/hydroxyl, oxetanes/amine, oxetanes/alcohol, isocyanates/hydroxyl, isocyanide Acid esters/amine, isocyanates/carboxylic acid, cyanate, acid anhydrides/amine, amine/carboxylic acid, amine/ester, hydroxyl/carboxylic acid, hydroxyl/acid chloride, amine/ Acid chloride, vinyl/Si-H, Si-Cl/ hydroxyl, Si-Cl/ amine, hydroxyl/aldehyde, amine/aldehyde, methylol or methylolamide/ Alcohol, aminoplast, alkynes/azide, click chemistry reactive group, alkene/sulphur, olefin/mercaptan, alkynes/mercaptan, hydroxyl Base/halide, isocyanates/water, Si-OH/ hydroxyl, Si-OH/ water, Si-OH/Si-H, Si-OH/Si-OH, perfluorovinyl sulfide, Diene/dienophile, olefin metathesis polymerisation group, olefinic polymerization group and ring-opening polymerisation base for ziegler-natta catalyzed Group and its mixture.
19. the described in any item methods of preceding claims, wherein the polymerizable liquid includes the component of photopolymerization, In step (a) after its photopolymerization (for example, heating thereafter) degrade and formed needed for the further curing schedule (d) at Point.
20. a kind of three-dimension object manufactured on carrier board by increasing material manufacturing, it includes:
(a) three-dimensional body part, the main part include carrier board contact-segment, and the contact-segment includes marginal portion；
(b) lip supports for connecting with the contact-segment and extending outward from the contact-segment marginal portion from the contact-segment Object, wherein the lip supports object forms on the carrier board and at least partially surrounding the contact-segment.
21. object described in claim 20, wherein the lip supports object includes carrier board contact-segment.
22. object described in claim 21, wherein the main part carrier board contact-segment and the lip supports object carrier Plate contact-segment is coplanar.
23. object described in claim 20 to 23, wherein the object is attached by the lip supports object and the contact-segment In carrier board.
CN201880020323.3A 2017-03-23 2018-03-22 It can be used for manufacturing the lip supports object of object by increasing material manufacturing Pending CN110520298A (en)

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